Accelerated ensemble generation for cyclic peptides using a Reservoir-REMD implementation in GROMACS

Author:

Hsueh Shawn C.C.ORCID,Aina Adekunle,Plotkin Steven S.

Abstract

AbstractCyclic peptides naturally occur as antibiotics, fungicides, and immunosuppressants, and have been adapted for use as potential therapeutics. Scaffolded cyclic peptide antigens have many protein characteristics such as reduced toxicity, increased stability over linear peptides, and conformational selectivity, but with fewer amino acids than whole proteins. The profile of shapes presented by a cyclic peptide modulates its therapeutic efficacy, and is represented by the ensemble of its sampled conformations. Although some algorithms excel in creating a diverse ensemble of cyclic peptide conformations, they seldom address the entropic contribution of flexible conformations, and they often have significant practical difficulty producing an ensemble with converged and reliable thermodynamic properties. In this study, an accelerated molecular dynamics (MD) method, reservoir replica exchange MD (R-REMD or Res-REMD), was implemented in GROMACS-4.6.7, and benchmarked on three small cyclic peptide model systems: a cyclized segment of Aβ (cyclo-(CGHHQKLVG)), a cyclized furin cleavage site of SARS-CoV-2 spike (cyclo-(CGPRRARSG)), and oxytocin (disulfide bonded CY-IQNCPLG). Additionally, we also benchmarked Res-REMD on Alanine dipeptide and Trpzip2 to demonstrate its validity and efficiency over REMD. Compared to REMD, Res-REMD significantly accelerated the ensemble generation of cyclo-(CGHHQKLVG), but not cyclo-(CGPRRARSG) or oxytocin. This difference is due to the longer auto-correlation time of torsional angles in cyclo-(CGHHQKLVG) v s. the latter two cyclic peptide systems; The randomly seeded reservoir in Res-REMD thus accelerates sampling and convergence. The auto-correlation time of the torsional angles can thus be used to determine whether Res-REMD is preferable to REMD for cyclic peptides. We provide a github page with modified GROMACS source code for running Res-REMD at https://github.com/PlotkinLab/Reservoir-REMD.

Publisher

Cold Spring Harbor Laboratory

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